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A series of prototypical Co(II)-based pyridyl bis(imine) complexes {[2- (ArN=C(Me)) 2 C 5 H 3 N]CoCl 2 } (Ar = 2,6-C 6 H 3 Me 2 , 2,5-C 6 H 3 Me 2 , 2,4-C 6 H 3 Me 2 , 2,3- C 6 H 3 Me 2 ) bearing two methyl substituents on each imine aryl group are studied as precatalysts for the homopolymerization of 1,3-butadiene. They showed very high polymerization activities associated with ethylaluminum sesquichloride (EAS) as a cocatalyst. The Co(II) catalysts containing less hindered pyridyl bis(imine) ligands, say [2-(2,3-C 6 H 3 Me 2 N=C(Me)) 2 C 5 H 3 N]CoCl 2  complex, showed highest activity to give high molecular weight polymers. All catalysts yielded  cis -1,4-polybutadienes up to 96.4% with  cis -1,4 regular structure.

Highly Stereospecific Polymerizations of 1,3-Butadiene with Cobalt(II) Pyridyl Bis(imine) Complexes